US5433261A - Methods for fabricating shapes by use of organometallic, ceramic precursor binders - Google Patents
Methods for fabricating shapes by use of organometallic, ceramic precursor binders Download PDFInfo
- Publication number
- US5433261A US5433261A US08/121,814 US12181493A US5433261A US 5433261 A US5433261 A US 5433261A US 12181493 A US12181493 A US 12181493A US 5433261 A US5433261 A US 5433261A
- Authority
- US
- United States
- Prior art keywords
- binder
- organometallic
- ceramic precursor
- sand
- hardenable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/205—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of organic silicon or metal compounds, other organometallic compounds
Definitions
- This invention relates to the discovery of organometallic ceramic precursor binders used to fabricate shaped bodies by different techniques.
- Exemplary shape making techniques which utilize hardenable, liquid, organometallic, ceramic precursor binders include the fabrication of negatives of parts to be made (e.g., sand molds and sand cores for metalcasting, etc.), as well as utilizing ceramic precursor binders to make shapes directly (e.g., brake shoes, brake pads, clutch parts, grinding wheels, polymer concrete, refractory patches and liners, etc.).
- this invention relates to thermosettable, liquid ceramic precursors which provide suitable-strength sand molds and sand cores at very low binder levels and which, upon exposure to molten metalcasting exhibit low emissions toxicity as a result of their high char yields of ceramic upon exposure to heat.
- Another preferred embodiment of the invention involves the fabrication of preforms used in the formation of composite articles.
- sand molds The casting of metal articles using sand molds, sand shells and sand cores is well known in the art. Detailed information regarding the state of this technology can be found, for example, in a text by James P. LaRue, EdD, Basic Metalcasting (The American Foundrymen's Society, Inc., Des Plaines, Ill., 1989).
- a mold can be made from a mixture of sand and (typically) an organic binder by packing the mixture loosely or tightly around a pattern. The pattern is then removed, leaving a cavity in the sand which replicates the shape of the pattern.
- the organic binder is shape-stabilized by any of a number of hardening techniques (as described below), the cavities in the sand mold are filled with molten metal by pouring the molten metal into the mold.
- binder-coated sand can be blown onto the interior surface of a heated metal pattern.
- the heat from the pattern penetrates the sand, producing a bond in the heat-affected layer.
- This layer clings to the pattern, and when the pattern is rotated, the sand not affected by the heat falls into a hopper for further use.
- the thin, bonded layer of binder-coated sand clinging to the pattern is then cured by heating.
- the cured shell is then pushed from the pattern by ejector pins. When a mating shell is produced, the shells are aligned and fastened together with a high-temperature adhesive for pouring.
- any holes or other internal shapes in a casting can be produced by using sand cores.
- cores are made from sand, numerous acceptable processes for making these cores are acceptable.
- a sand mixture comprising a binder material is placed into a corebox. There, the sand mixture takes the shape of the cavity in the box, becomes hard, and is removed.
- the core is then set in the "drag" just before the mold is closed.
- the metal is poured, the molten metal fills the mold cavity except for where sand cores are present.
- the shape of the solidified casting results from the combined shapes of the mold and the sand core(s).
- binder materials are now available for making cores. These binder materials can be categorized as vapor-cured (cured by a gas of some kind), heat-cured (cured by heat), or no-bake (cured by chemical reaction).
- char should be understood as meaning the solid products of binder decomposition which remain after thermal treatment during the metalcasting process. They do, however, have certain disadvantages.
- Vapor-cured sodium silicate binders for example, are typically processed by coating sand grains with the sodium silicate binder, backing the mixture into a corebox, and then gassing the mixture in the corebox with carbon dioxide for a short period of time (about 10 seconds). This treatment hardens the core, allowing it to be removed from the corebox.
- One advantage of this system is that the core can be used immediately.
- a major disadvantage of such systems is the tendency for the resulting cores to absorb moisture. Many of the inorganic resin systems currently in use share this problem.
- Vapor-cured systems include the phenolic urethane/amine binders, phenolic esters, furan/peroxide systems which, typically, are acid cured, and epoxy/sulfur dioxide systems.
- Heat-cured systems include phenolic resins, furan systems, and urea formaldehyde binders.
- No-bake systems comprise acid-cured furan systems, acid-cured phenolic resins, alkyd oil urethanes, phenolic urethanes, and phenolic esters.
- Organometallic, ceramic precursors are known in the art of ceramic processing. These materials can be in the form of either solvent-soluble solids, meltable solids, or hardenable liquids, all of which permit the processibility of their organic counterparts in the fabrication of ceramic "green bodies".
- the ceramic precursor binders have the added advantage of contributing to the overall ceramic content of the finished part, because the thermal decomposition of such ceramic precursor binders results in relatively high yields of ceramic "char".
- This second feature is advantageous, for example, in reducing part shrinkage and the amount of voids present in the fired part, thereby reducing the number of critically sized flaws which have been shown to result in strength degradation of formed bodies.
- Such precursors can be monomeric, oligomeric, or polymeric and can be characterized generally by their processing flexibility and high char yields of ceramic material upon thermal decomposition (i.e. pyrolysis). These precursors are neither wholly inorganic nor wholly organic materials, since they comprise metal-carbon bonds. These precursors can be distinguished from other known inorganic binders for sand mold fabrication described above (which comprise no carbon), and other known organic binders (which comprise no metallic elements). It has been unexpectedly discovered that such organometallic "hybrids" which are hardenable liquids are uniquely suited for use as binders for sand grains in the fabrication of sand molds, cores, and shells, since they can provide excellent mold strength at extremely low binder levels.
- organometallic "hybrids” have been found to be uniquely suited to the formation of metal matrix composites by molten metal infiltration processes (e.g., spontaneous infiltration, pressure and vacuum assisted infiltration, etc.). Moreover, these organometallic "hybrids” have also been found to be useful as preform binders for ceramic matrix composite formation processes (e.g., directed metal oxidation, sintering, isostatic pressing, chemical vapor infiltration, etc.). Further, since such organometallic, ceramic precursor binders are also liquids, they can be employed directly without use of a solvent. This obviates the emissions and disposal problems associated with solvent-based systems which require a "drying" step subsequent to mold shaping.
- Siloxanes have been used in the past to improve the adhesion of such binder systems as polycyanoacrylates to sand grains (see, for example, U.S. Pat. No. 4,076,685). In such a system the siloxane is used as a processing aid rather than the binder itself. Additionally, partial condensates of trisilanols have been used in combination with silica as binder systems which are provided in aliphatic alcohol-water cosolvent (see, for example, U.S. Pat. No. 3,898,090). Such in-solvent binders have been shown to suffer the disadvantage of short shelf life ("several days") due to additional silanol condensation during storage.
- a further disadvantage is that these binders require the step of solvent removal from the core or mold by a drying process ("to remove a major portion of the alcohol-water cosolvent") before metalcasting. Otherwise, voids and poor mold integrity result during the metalcasting process.
- a drying process to remove a major portion of the alcohol-water cosolvent
- This invention relates to the discovery of organometallic ceramic precursor binders used to fabricate shaped bodies by different techniques.
- Exemplary shape making techniques which utilize hardenable, liquid, organometallic, ceramic precursor binders include the fabrication of negatives of parts to be made (e.g., sand molds and sand cores for metalcasting, etc.), as well as utilizing ceramic precursor binders to make shapes directly (e.g., brake shoes, brake pads, clutch parts, grinding wheels, polymer concrete, refractory patches, liners, and preforms of various components for further processing, etc.).
- a preferred embodiment of the invention relates to the fabrication of shaped metal, or metal matrix composite, articles by metalcasting into sand molds, shells or sand cores prepared using hardenable, liquid, organometallic, ceramic precursor binders.
- the method comprises (1) solventless coating of the surface of sand with a hardenable, liquid, organometallic, ceramic precursor binder, (2) forming a shape from said sand/binder mixture, (3) hardening said binder to form a sand mold, shell, or core, and (4) metalcasting into the resulting hardened sand mold, shell, or core to form a shaped metal article.
- binder levels as low as 0.1 wt % of a polyureasilazane comprising crosslinkable vinyl groups result in sand molds which have excellent strength in metalcasting operations.
- a predetermined quantity of sand is coated by mixing the sand with an organometallic, ceramic precursor binder in an amount sufficient to result in a hardened sand mold, shell, or core having suitable strength for ease of handling, as well as sufficient structural integrity needed for the metalcasting process.
- the aforementioned sufficient strength should not be too great so as to deleteriously impact the ability to remove a cast metal part from a sand mold (e.g., by physically breaking the sand mold away from the cast part).
- the sand/binder mixture is then shaped using standard procedures for preparing metalcasting molds, shells, or cores and then hardened using a procedure suited to the exact chemical composition of the organometallic, ceramic precursor binder.
- the hardened mold, shell, or core is then used to pour a shaped metal object by a metalcasting process. It should be understood that while this disclosure refers primarily to a metalcasting process, the concepts of this disclosure also apply to the casting of metal matrix composite articles.
- Another preferred embodiment of the invention relates to the use of organometallic ceramic precursor binders in the fabrication of preforms used in the formation of composite articles, such as ceramic composite articles and metal matrix composite articles.
- organometallic ceramic precursor binders may be used to form preforms to be used in the fabrication of metal matrix composite articles by a pressureless metal infiltration process described, for example, in commonly owned U.S. Pat. No. 5,249,621, which issued Oct. 5, 1993, in the names of Aghajanian et al. and entitled "Method of Forming Metal Matrix Composite Bodies by a Spontaneous Infiltration Process and Products Produced Therefrom" from U.S. patent application Ser. No. 07/863,894, filed Apr. 6, 1992, which is a continuation application of U.S. patent application Ser. No.
- the method comprises (1) providing a solventless coating on at least a portion of the surface of a filler material with a hardenably liquid, organometallic, ceramic precursor binder, (2) optionally incorporating an infiltration enhancer and/or an infiltration enhancer precursor with the solventless coated filler material, (3) forming a shape from the filler material/binder mixture, optionally containing an infiltration enhancer precursor and/or an infiltration enhancer, (4) hardening said binder to form a permeable preform, and (5) spontaneously infiltrating the resulting permeable preform using the methods described in commonly owned U.S. Pat. No. 5,249,621 to form a shaped metal article.
- binder levels as low as 0.1 weight percent of a polyureasilazane comprising crosslinkable vinyl groups result in preforms which have excellent strength for use in the pressureless metal infiltration process.
- binder levels from about 0.5 weight percent to about 3 weight percent of a polyureasilazane may be used.
- a predetermined quantity of filler material is coated by mixing the filler material with an organometallic, ceramic precursor binder in an amount sufficient to result in a hardened preform having suitable strength for ease of handling, as well as sufficient structural integrity needed for the pressureless metal infiltration process.
- the hardened preform is then used in the pressureless metal infiltration process to form the metal matrix composite article.
- the concept of this disclosure also applies to formation of metal matrix composite articles by, for example, pressure infiltration, vacuum-assisted infiltration, etc.
- FIG. 1 is a photograph of the cast aluminum alloy piece and the sand mold formed in Example 5.
- FIG. 2 is a photograph of the cast iron piece and the sand mold formed in Example 7.
- This invention relates to the discovery of organometallic ceramic precursor binders used to fabricate shaped bodies by different techniques.
- Exemplary shape making techniques which utilize hardenable, liquid, organometallic, ceramic precursor binders include the fabrication of negatives of parts to be made (e.g., sand molds and sand cores for metalcasting, etc.), as well as utilizing ceramic precursor binders to make shapes directly (e.g., brake shoes, brake pads, clutch parts, grinding wheels, polymer concrete, refractory patches, liners, and preforms for various components for further processing, etc.).
- organometallic, ceramic precursor binders suitable for the practice of this invention include monomers, oligomers and polymers.
- organometallic should be understood as meaning a composition comprising a metal-carbon bond.
- Suitable metals include both main group and transition metals selected from the group consisting of metals and metalloids selected from IUPAC groups 1 through 15 of the periodic table of elements inclusive.
- Preferred metals/metalloids include titanium, zirconium, silicon and aluminum, with silicon being a preferred selection.
- monomeric ceramic precursors can satisfy the requirements necessary for the practice of this invention, monomers that polymerize to form hard polymers of appreciable ceramic yield (e.g., greater than 20 percent by weight) often have so low a molecular weight that volatilization at modest molding temperatures becomes a problem.
- One example of this is vinyltrimethylsilane, which has a boiling point of only 55° C. Curing this monomer by thermal or radical means to form a hardened binder requires temperatures greater than the boiling point of the monomer. It is thus unsuitable in the process described. Because monomers are generally too volatile to be used in this molding process, the preferred liquid ceramic precursors of this invention are either oligomeric or polymeric.
- An oligomer is defined as a polymer molecule consisting of only a few monomer repeat units (e.g., greater than two and generally less than 30) while a polymer has monomer repeat units in excess of 30.
- Suitable polymers include, for example, but should not be construed as being limited to polysilazanes, polyureasilazanes, polythioureasilazanes, polycarbosilanes, polysilanes, polysiloxanes, polyborosilazanes, polyaminosilazanes and polyaminoboranes.
- Precursors to oxide ceramics such as aluminum oxide as well as non-oxide ceramics can also be used.
- Organometallic, ceramic precursors suitable for the practice of this invention should have char yields in excess of 20 percent by weight, preferably in excess of 40 percent by weight, and more preferably in excess of 50 percent by weight when the hardened precursor is thermally decomposed.
- the organometallic, ceramic precursors suitable for the practice of this invention preferably contain sites of organounsaturation such as alkenyl, alkynyl, epoxy, acrylate or methacrylate groups. Such groups may facilitate hardening when energy in the form of heat, UV irradiation, or laser energy is provided to promote a free radical or ionic crosslinking mechanism or the organounsaturated groups. Such crosslinking reactions promote rapid hardening and result in hardened binders having higher ceramic yields upon pyrolysis. High ceramic yield typically results in lower volatiles evolution during metalcasting.
- organounsaturation such as alkenyl, alkynyl, epoxy, acrylate or methacrylate groups.
- groups may facilitate hardening when energy in the form of heat, UV irradiation, or laser energy is provided to promote a free radical or ionic crosslinking mechanism or the organounsaturated groups.
- Such crosslinking reactions promote rapid hardening and result in hardened binders having higher
- Such precursors include poly(acryloxypropylmethyl)siloxane, glycidoxypropylmethyldimethylsiloxane copolymer, polyvinylmethylsiloxane, poly(methylvinyl)silazane, 1,2,5-trimethyl-1,3,5-trivinyltrisilazane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyltetrasilazane, 1,3,5-tetravinyltetramethylcyclotetrasiloxane, tris(vinyldimethylsiloxy)methylsilane, and trivinylmethylsilane.
- a free radical generator such as a peroxide or azo compound, may, optionally, be added to promote rapid hardening at a low temperature.
- Exemplary peroxides for use in the present invention include, for example, diaroyl peroxides such as dibenzoyl peroxide, di p-chlorobenzoyl peroxide, and bis-2,4-dichlorobenzoyl peroxide; dialkyl peroxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and di t-butyl peroxide; diaralkyl peroxides such as dicumyl peroxide; alkyl aralkyl peroxides such as t-butyl cumyl peroxide and 1,4-bis(t-butylperoxyisopropyl)benzene; alkylaroyl peroxides and alkylacyl peroxides such as t-butyl perbenzoate, t-butyl peracetate, and t-butyl peroctoate.
- diaroyl peroxides such as dibenzoyl
- peroxysiloxanes as described, for example, in U.S. Pat. No. 2,970,982 (the subject matter of which is herein incorporated by reference) and peroxycarbonates such as t-butylperoxy isopropyl carbonate.
- Symmetrical or unsymmetrical azo compounds such as the following, may be used as free radical generators: 2,2'-azobis(2-methylpropionitrile); 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile); 1-cyano-1-(t-butylazo)cyclohexane; and 2-(t-butylazo)isobutyronitrile.
- 2,2'-azobis(2-methylpropionitrile) 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile)
- 1-cyano-1-(t-butylazo)cyclohexane and 2-(t-butylazo)isobutyronitrile.
- crosslinking which may be provided through sites of organounsaturation which are appended to the organometallic, ceramic precursor binder
- additional modes of crosslinking provided by polymer chain condensation upon pyrolysis may be beneficial.
- silicon polymers comprising nitrogen are preferred to silicon polymers comprising oxygen, since nitrogen is trivalent.
- the repeat unit of the polymer chain contains Si--N bonds in which the nitrogen atom is then further bonded both to either two addition silicon atoms, or a silicon atom and a carbon or hydrogen atom.
- such polysilazanes crosslink via N--C or N--H bond cleavage with subsequent crosslinking provided by formation of an additional Si--N bond.
- Such crosslinking provides for higher char yields upon binder hardening. This leads to lower volatiles evolution during metalcasting when such polymers are used as binders for the sand mold, shells, or cores which are used.
- the known method of coating the sand with the liquid, organometallic, ceramic precursor can be used. Such methods comprise, but are not limited to simple hand mixing, mulling, milling, etc.
- the amount of organometallic, ceramic precursor binder used in coating should be such that the strength of the hardened, molded sand object is sufficient to provide for easy handling and also sufficient to ensure structural integrity of the mold during the metalcasting process.
- the amount of organometallic, ceramic precursor binder utilized in the formation of preforms for composite article fabrication should allow for ease of handling and sufficient structural integrity during the composite formation process.
- suitable organometallic ceramic precursors can be quite low.
- binder levels can be in the range of 0.1% to about 20% based on the total weight of the sand/binder mixture or the filler material/binder mixture, preferably 0.1 wt % to 5 wt %, and more preferably 0.1 wt % to 2 wt % of binder should be used.
- binder levels can be in the range of 0.1% to about 20% based on the total weight of the sand/binder mixture or the filler material/binder mixture, preferably 0.1 wt % to 5 wt %, and more preferably 0.1 wt % to 2 wt % of binder should be used.
- highly crosslinkable organometallic, ceramic precursor binders are used, the lowest levels of binder can be achieved.
- the sand/binder mixture can be formed into molds, shells, or cores by any technique known in the art. Binder hardening is then accomplished by vapor arc, heat arc, chemical cure and/or combinations thereof.
- the organometallic ceramic precursor binder comprises a site of organounsaturation such as a vinyl group which can be crosslinked by thermal treatment to harden the binder.
- a free radical initiator can be added to the composition to facilitate the free radical crosslinking of the binder which serves to harden irreversibly the composition.
- a temperature is generally selected so that the hardening time is greater or equal to one or preferably two half lives of the initiator at that temperature. It is important for the sand/binder mixture to harden sufficiently so that ease of handling and metalcasting can be ensured.
- Suitable free radical initiators include, but are not limited to, organic peroxides, inorganic peroxides, and azo compounds.
- the sand molds, shells, and cores can then be used for metalcasting.
- Typical metals suitable for such application include aluminum, aluminum alloys, iron, ferrous alloys and composites including such metals as the matrix.
- Another preferred embodiment of the invention relates to the use of organometallic ceramic precursor binders in the fabrication of preforms used in the formation of composite articles, and particularly metal matrix composite articles made by the pressureless metal infiltration process described in, for example, commonly owned U.S. Pat. No. 5,249,621, which issued Oct. 5, 1993, in the names of Aghajanian et al. and entitled "Method of Forming Metal Matrix Composite Bodies by a Spontaneous Infiltration Process and Products Produced Therefrom" from U.S. patent application Ser. No. 07/863,894, filed Apr. 6, 1992, which is a continuation application of U.S. patent application Ser. No.
- the method for forming a metal matrix composite comprises (1) providing a solventless coating on the surface of a filler material with a hardenable liquid, organometallic, ceramic precursor binder, (2) optionally incorporating an infiltration enhancer and/or an infiltration enhancer precursor with the solventless coated filler material, (3) forming a shape from the filler material/binder mixture, (4) hardening said binder to form a preform, and (5) spontaneously infiltrating the resulting preform using the methods described in U.S. Pat. No. 5,249,621 to form a shaped metal matrix article.
- binder levels as low as 0.1 weight percent of a polyureasilazane comprising crosslinkable vinyl groups result in preforms which have excellent strength for use in the pressureless metal infiltration process.
- binder levels from about 0.5 weight percent to about 3 weight percent of a polyureasilazance may be used.
- a predetermined quantity of filler material is coated by mixing the filler material with an organometallic, ceramic precursor binder in an amount sufficient to result in a hardened preform having suitable strength for ease of handling, as well as sufficient structural integrity needed for the pressureless metal infiltration process.
- the hardened preform is then used in the pressureless metal infiltration process to form the metal matrix composite article.
- this disclosure refers primarily to forming metal matrix composite bodies by the pressureless metal infiltration process, the concept of this disclosure also applied to formation of metal matrix composite articles by, for example, pressure infiltration, vacuum-assisted infiltration, etc.
- This Example demonstrates a method for fabricating a sand mold for metalcasting using a Polyureasilazane in accordance with the present invention.
- the crucible was held at this temperature for about 1 hour, and the temperature was then raised to about 140° C. for about 0.5 hour.
- the vessel was allowed to cool to room temperature.
- the polymer/sand mixture had hardened in the crucible, and replicated the exact shape of the crucible.
- the molded piece could be sanded to a new shape by rubbing with coarse silicon carbide abrasive cloth.
- the hardened 4 percent by weight part could be dropped or thrown against a table top without visible damage.
- This Example demonstrates the use of differing binder amounts in a sand mold fabricated in accordance with the present invention.
- Example 2 Polymer sand mixtures were prepared at the 0.5 percent by weight and 1 percent by weight polymer levels. About 20 gram samples were loaded into crucibles and cured according to the heating schedule of Example 1. The following observations were noted. The cured 1.0 percent by weight part could be dropped or thrown onto the table top with only slight visible edge damage. The 0.5 percent by weight cured part could be crumbled by hand using considerable effort.
- Substantially the same procedure used in Example 1 was used to prepare a hardened part comprising 4 percent by weight poly(methylvinyl)silazane binder prepared by the ammonolysis of an 80:20 molar ratio mixture of methyldichlorosilane to vinylmethyldichlorosilane in hexane solvent according to procedures detailed in Example 1 of U.S. Pat. No. 4,929,704.
- the part could be dropped or thrown against a table top without visible damage.
- This Example demonstrates a method for fabricating a sand mold for metal casting in accordance with the present invention.
- Dicumyl peroxide (about 1.2 gram) was dissolved in the polyureasilazane polymer described in Example 1 (about 24 grams).
- Washed silica sand (about 1176 grams, Wedron Silica Co., Wedron, Ill.) was slowly mixed into the polymer/peroxide blend to form an about 2 percent by weight polymer/sand mixture.
- This 2 percent by weight binder/sand mixture was packed into a rubber mold containing a positive definition well for metal casting.
- the binder/sand mixture was cured in an air atmosphere oven at about 100° C. for a period of about 30 minutes, the temperature was raised to about 110° C. for about 1 hour, and then raised to about 125° C. for about 1 hour.
- the mold was cooled to room temperature and the sand was demolded. The sand replicated the shape of the mold.
- This Example demonstrates a method for fabricating a sand mold for metal casting and thereafter casting molten aluminum alloy into the cavity of the sand mold.
- Dicumyl peroxide (about 0.6 gram) was dissolved in the polyureasilazane polymer described in Example 1 (about 12 grams).
- Washed silica sand (about 1176 grams, Wedron Silica Co., Wedron, Ill.) was slowly mixed into the polymer/peroxide blend to form a 1 percent by weight polymer/sand mixture.
- This 1 percent by weight binder/sand mixture was packed into a rubber mold containing a positive definition well for metal casting.
- the binder/sand mixture was cured in an air atmosphere oven at about 100° C. for a period of about 30 minutes, the temperature was raised to about 110° C. for about 1 hour, and then raised to about 125° C. for about 1 hour.
- the mold was cooled to room temperature and the sand was demolded. The sand replicated the shape of the mold.
- the cured mold was then placed on a table and an aluminum alloy comprising about 10% silicon by weight, balance aluminum, was melted and raised to a temperature of about 700° C. After stabilizing the temperature of the molten aluminum alloy at about 700° C., a ladle was dipped into the molten aluminum alloy and a small sample of the aluminum alloy was slowly poured into the cavity of the mold and the aluminum alloy was allowed to cool to room temperature.
- FIG. 1 is a photograph of the cast aluminum alloy part and the mold.
- This Example demonstrates. a method for fabricating a sand mold for metal casting and thereafter casting molten aluminum alloy around the sand mold.
- Dicumyl peroxide (about 1.2 gram) was dissolved in the polyureasilazane polymer described in Example 1 (about 24 grams).
- Washed silica sand (about 1176 grams, Wedron Silica Co., Wedron, Ill.) was slowly mixed into the polymer/peroxide blend to form a 2 percent by weight polymer/sand mixture.
- This 2 percent by weight binder/sand mixture was packed into a rubber mold containing a positive definition well for metal casting.
- the binder/sand mixture was cured in an air atmosphere oven at about 100° C. for a period of about 30 minutes, the temperature was raised to about 110° C. for about 1 hour, and then raised to about 125° C. for about 1 hour.
- the mold was cooled to room temperature and the sand was demolded. The sand replicated the shape of the mold.
- the cured sand mold was placed into a graphite mold having a cavity measuring about 7 inches by 7 inches by 1 inch.
- An aluminum alloy comprising about 10% by weight silicon, balance aluminum, was melted and maintained at a temperature of about 700° C.
- a ladle was dipped into the molten aluminum and a small sample of the aluminum alloy was poured into the graphite mold, around the cured sand mold, but not into its cavity, and allowed to cool to room temperature.
- This Example demonstrates a method for fabricating a sand mold for metal casting and thereafter casting molten cast iron into the cavity of the sand mold.
- Dicumyl peroxide (about 0.6 gram) was dissolved in the polyureasilazane polymer described in Example 1 (about 12 grams).
- Washed silica sand (about 1176 grams, Wedron Silica Co., Wedron, Ill.) was slowly mixed into the polymer/peroxide blend to form a 1 percent by weight polymer/sand mixture.
- This 1 percent by weight binder/sand mixture was packed into a rubber mold containing a positive definition well for metal casting.
- the binder/sand mixture was cured in an air atmosphere oven at about 100° C. for a period of about 30 minutes, the temperature was raised to about 110° C. for about 1 hour, and then raised to about 125° C. for about 1 hour.
- the mold was cooled to room temperature and the sand was demolded. The sand replicated the shape of the mold.
- FIG. 2 is a photograph of the cooled cast iron piece and the sand mold.
- This Example demonstrates a method for fabricating a sand mold for metal casting and thereafter casting molten cast iron around the sand mold.
- Dicumyl peroxide (about 1.2 grams) was dissolved in the polyureasilazane polymer described in Example 1 (about 24 grams).
- Washed silica sand (about 1176 grams, Wedron Silica Co., Wedron, Ill.) was slowly mixed into the polymer/peroxide blend to form a 2 percent by weight polymer/sand mixture.
- This 2 percent by weight binder/sand mixture was packed into a rubber mold containing a positive definition well for metal casting.
- the binder/sand mixture was cured in an air atmosphere oven at about 100° C. for a period of about 30 minutes, the temperature was raised to about 110° C. for about 1 hour, and then raised to about 125° C. for about 1 hour.
- the mold was cooled to room temperature and the sand was demolded. The sand replicated the shape of the mold.
- the cured sand piece was placed into a steel frame having a cavity of about 6 inches by 5 inches.
- a quantity of cast iron was melted in a small crucible and maintained at a temperature of about 1350° C.
- the cast iron was then poured from the crucible into the steel frame and around the cured sand piece, but not into its cavity, and allowed to cool to room temperature.
Abstract
Description
Claims (20)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/121,814 US5433261A (en) | 1993-04-30 | 1993-09-15 | Methods for fabricating shapes by use of organometallic, ceramic precursor binders |
US08/482,698 US5641817A (en) | 1993-04-30 | 1995-06-07 | Methods for fabricating shapes by use of organometallic, ceramic precursor binders |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US5565493A | 1993-04-30 | 1993-04-30 | |
US08/121,814 US5433261A (en) | 1993-04-30 | 1993-09-15 | Methods for fabricating shapes by use of organometallic, ceramic precursor binders |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US5565493A Continuation-In-Part | 1993-04-30 | 1993-04-30 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/482,698 Continuation-In-Part US5641817A (en) | 1993-04-30 | 1995-06-07 | Methods for fabricating shapes by use of organometallic, ceramic precursor binders |
Publications (1)
Publication Number | Publication Date |
---|---|
US5433261A true US5433261A (en) | 1995-07-18 |
Family
ID=21999305
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/121,814 Expired - Lifetime US5433261A (en) | 1993-04-30 | 1993-09-15 | Methods for fabricating shapes by use of organometallic, ceramic precursor binders |
US08/535,121 Expired - Fee Related US5884688A (en) | 1993-04-30 | 1994-04-28 | Methods for fabricating shapes by use of organometallic ceramic precursor binders |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/535,121 Expired - Fee Related US5884688A (en) | 1993-04-30 | 1994-04-28 | Methods for fabricating shapes by use of organometallic ceramic precursor binders |
Country Status (6)
Country | Link |
---|---|
US (2) | US5433261A (en) |
EP (1) | EP0695226B1 (en) |
JP (1) | JPH08509665A (en) |
CA (1) | CA2157009A1 (en) |
DE (1) | DE69404456T2 (en) |
WO (1) | WO1994025199A1 (en) |
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5837047A (en) * | 1996-12-11 | 1998-11-17 | Ashland Inc. | Heat curable binder systems and their use |
US6147138A (en) * | 1997-06-06 | 2000-11-14 | Generis Gmbh | Method for manufacturing of parts by a deposition technique |
US20030233923A1 (en) * | 2002-06-20 | 2003-12-25 | Eu-Pin Wang | Woodworking drill |
US20040250653A1 (en) * | 1999-07-20 | 2004-12-16 | Dwivedi Ratnesh K. | Microporous metal parts |
US20080158173A1 (en) * | 2007-01-03 | 2008-07-03 | Apple Computer, Inc. | Multi-touch surface stackup arrangement |
US20090282528A1 (en) * | 2008-05-09 | 2009-11-12 | Monsanto Technology Llc | Plants and seeds of hybrid corn variety ch619141 |
US9649812B2 (en) | 2011-01-05 | 2017-05-16 | Voxeljet Ag | Device and method for constructing a laminar body comprising at least one position-adjustable body defining the working area |
US9656423B2 (en) | 2010-03-31 | 2017-05-23 | Voxeljet Ag | Device and method for producing three-dimensional models |
US9770867B2 (en) | 2010-12-29 | 2017-09-26 | Voxeljet Ag | Method and material system for building models in layers |
US9863254B2 (en) | 2012-04-23 | 2018-01-09 | General Electric Company | Turbine airfoil with local wall thickness control |
US9914169B2 (en) | 2010-04-17 | 2018-03-13 | Voxeljet Ag | Method and device for producing three-dimensional models |
US9943981B2 (en) | 2013-12-11 | 2018-04-17 | Voxeljet Ag | 3D infiltration method |
US9962885B2 (en) | 2010-04-14 | 2018-05-08 | Voxeljet Ag | Device for producing three-dimensional models |
US10052682B2 (en) | 2012-10-12 | 2018-08-21 | Voxeljet Ag | 3D multi-stage method |
US10059062B2 (en) | 2012-05-25 | 2018-08-28 | Voxeljet Ag | Device for producing three-dimensional models with special building platforms and drive systems |
US10059058B2 (en) | 2012-06-22 | 2018-08-28 | Voxeljet Ag | Device for building a multilayer structure with storage container or filling container movable along the dispensing container |
US10213831B2 (en) | 2012-11-25 | 2019-02-26 | Voxeljet Ag | Construction of a 3D printing device for producing components |
US10220567B2 (en) | 2012-03-06 | 2019-03-05 | Voxeljet Ag | Method and device for producing three-dimensional models |
US10220568B2 (en) | 2013-12-02 | 2019-03-05 | Voxeljet Ag | Interchangeable container with moveable side walls |
US10226919B2 (en) | 2007-07-18 | 2019-03-12 | Voxeljet Ag | Articles and structures prepared by three-dimensional printing method |
US10343301B2 (en) | 2013-02-28 | 2019-07-09 | Voxeljet Ag | Process for producing a moulding using a water-soluble casting mould and material system for the production thereof |
US10442170B2 (en) | 2013-12-20 | 2019-10-15 | Voxeljet Ag | Device, special paper, and method for producing shaped articles |
US10682809B2 (en) | 2014-12-22 | 2020-06-16 | Voxeljet Ag | Method and device for producing 3D moulded parts by means of a layer construction technique |
US10786945B2 (en) | 2013-10-30 | 2020-09-29 | Voxeljet Ag | Method and device for producing three-dimensional models using a binding agent system |
US10843404B2 (en) | 2015-05-20 | 2020-11-24 | Voxeljet Ag | Phenolic resin method |
US10882110B2 (en) | 2015-09-09 | 2021-01-05 | Voxeljet Ag | Method and device for applying fluids |
US10913207B2 (en) | 2014-05-26 | 2021-02-09 | Voxeljet Ag | 3D reverse printing method and device |
US10946556B2 (en) | 2014-08-02 | 2021-03-16 | Voxeljet Ag | Method and casting mold, in particular for use in cold casting methods |
US11097469B2 (en) | 2012-10-15 | 2021-08-24 | Voxeljet Ag | Method and device for producing three-dimensional models with a temperature-controllable print head |
US11097471B2 (en) | 2014-03-31 | 2021-08-24 | Voxeljet Ag | Method and device for 3D printing using temperature-controlled processing |
US11235518B2 (en) | 2015-12-01 | 2022-02-01 | Voxeljet Ag | Method and device for producing three-dimensional components with the aid of an overfeed sensor |
US11890810B2 (en) | 2015-09-16 | 2024-02-06 | Voxeljet Ag | Device and method for producing three-dimensional shaped parts |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ZA956408B (en) * | 1994-08-17 | 1996-03-11 | De Beers Ind Diamond | Abrasive body |
DE19647368A1 (en) * | 1996-11-15 | 1998-05-20 | Inst Neue Mat Gemein Gmbh | Composites |
ES2230086T3 (en) | 2000-03-24 | 2005-05-01 | Voxeljet Technology Gmbh | METHOD AND APPLIANCE FOR MANUFACTURING A STRUCTURAL PART BY MULTI-LAYER DEPOSITION TECHNIQUE AND MALE MOLDING MANUFACTURED WITH THE METHOD. |
US7098275B2 (en) * | 2001-06-27 | 2006-08-29 | Inglefield Charles F | Heat resistant material for molds and other articles |
US6638572B1 (en) | 2001-06-27 | 2003-10-28 | Charles F. Inglefield | Heat resistant material for molds and other articles |
US20030041525A1 (en) * | 2001-08-31 | 2003-03-06 | Sherwood Walter J. | Ceramic bonded abrasive |
US7488537B2 (en) | 2004-09-01 | 2009-02-10 | Radtke Robert P | Ceramic impregnated superabrasives |
US20080135721A1 (en) * | 2006-12-06 | 2008-06-12 | General Electric Company | Casting compositions for manufacturing metal casting and methods of manufacturing thereof |
DE102007050953A1 (en) | 2007-10-23 | 2009-04-30 | Voxeljet Technology Gmbh | Device for the layered construction of models |
DE102010006939A1 (en) | 2010-02-04 | 2011-08-04 | Voxeljet Technology GmbH, 86167 | Device for producing three-dimensional models |
US10111282B2 (en) | 2011-07-25 | 2018-10-23 | Ivoclar Vivadent Ag | Dental furnace |
EP2550928B1 (en) * | 2011-07-25 | 2017-03-01 | Ivoclar Vivadent AG | Dental oven with a drying sensor |
DE102011111498A1 (en) | 2011-08-31 | 2013-02-28 | Voxeljet Technology Gmbh | Device for the layered construction of models |
DE102015003372A1 (en) | 2015-03-17 | 2016-09-22 | Voxeljet Ag | Method and device for producing 3D molded parts with double recoater |
DE102016013610A1 (en) | 2016-11-15 | 2018-05-17 | Voxeljet Ag | Intra-head printhead maintenance station for powder bed-based 3D printing |
DE102017006860A1 (en) | 2017-07-21 | 2019-01-24 | Voxeljet Ag | Method and device for producing 3D molded parts with spectrum converter |
DE102019000796A1 (en) | 2019-02-05 | 2020-08-06 | Voxeljet Ag | Exchangeable process unit |
DE102019007595A1 (en) | 2019-11-01 | 2021-05-06 | Voxeljet Ag | 3D PRINTING PROCESS AND MOLDED PART MANUFACTURED WITH LIGNINE SULPHATE |
Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2492763A (en) * | 1946-10-30 | 1949-12-27 | Du Pont | Azobis (alpha-cycloalkyl-acetonitriles) |
US2515628A (en) * | 1946-03-16 | 1950-07-18 | Du Pont | Aliphatic-cyano-azo compounds |
US2970982A (en) * | 1961-02-07 | Diorganopolysiloxanes of low vola- | ||
US3093494A (en) * | 1961-06-12 | 1963-06-11 | Dow Corning | Preparation of molded articles |
US3432312A (en) * | 1965-09-08 | 1969-03-11 | Howmet Corp | Refractory mold composition and method |
US3898090A (en) * | 1974-06-24 | 1975-08-05 | Dow Corning | Foundry mold and core compositions |
US4076685A (en) * | 1972-01-25 | 1978-02-28 | Ashland Oil, Inc. | Cyanoacrylate foundry binders and process |
US4357165A (en) * | 1978-11-08 | 1982-11-02 | The Duriron Company | Aluminosilicate hydrogel bonded granular compositions and method of preparing same |
US4526219A (en) * | 1980-01-07 | 1985-07-02 | Ashland Oil, Inc. | Process of forming foundry cores and molds utilizing binder curable by free radical polymerization |
US4602069A (en) * | 1984-04-11 | 1986-07-22 | Ashland Oil, Inc. | Phenolic resin-polyisocyanate binder systems containing a phosphorus based acid |
US4775704A (en) * | 1987-04-22 | 1988-10-04 | Teiji Nagahori | Mold material for forming sandmold without requiring mold wash |
US4894254A (en) * | 1987-11-17 | 1990-01-16 | Tokyo Ohka Kogyo Co., Ltd. | Method of forming silicone film |
US4929704A (en) * | 1988-12-20 | 1990-05-29 | Hercules Incorporated | Isocyanate- and isothiocyanate-modified polysilazane ceramic precursors |
US5138014A (en) * | 1988-12-20 | 1992-08-11 | Mitsubishi Kasei Corporation | Silicate compound modified by hydroxyl containing compounds |
US5167271A (en) * | 1988-10-20 | 1992-12-01 | Lange Frederick F | Method to produce ceramic reinforced or ceramic-metal matrix composite articles |
US5183096A (en) * | 1990-03-15 | 1993-02-02 | Cook Arnold J | Method and apparatus for single die composite production |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB790685A (en) * | 1953-12-07 | 1958-02-12 | Jean Bellezanne | Refractory binder chiefly for wax and the like moulding methods |
BE635972A (en) * | 1963-08-06 | |||
SU432964A1 (en) * | 1970-01-07 | 1974-06-25 | MIXTURE FOR THE MANUFACTURE OF CASTING FORMS * AND RODS | |
GB2040295B (en) * | 1978-11-24 | 1983-03-23 | V Ni I Pi Tekhnol Khim I Nefty | Moulding sand mixture for the manufacture of moulds and cores |
DE3203546A1 (en) * | 1982-02-03 | 1983-08-11 | Dynamit Nobel Ag, 5210 Troisdorf | BINDERS CONTAINING TITANIC ACID ESTERS FOR COATING MEASURES AND FIRE-RESISTANT MOLDED BODIES, AND METHOD FOR THE PRODUCTION OF THESE BINDERS |
JPH0815636B2 (en) * | 1986-07-29 | 1996-02-21 | 日産化学工業株式会社 | Binder for precision mold making |
US4942145A (en) * | 1989-05-26 | 1990-07-17 | Ethyl Corporation | Preceramic compositions and ceramic products |
JPH03119062A (en) * | 1989-09-30 | 1991-05-21 | Tonen Corp | Binder comdsition |
JPH0524939A (en) * | 1991-07-16 | 1993-02-02 | Showa Electric Wire & Cable Co Ltd | Refractory castable |
-
1993
- 1993-09-15 US US08/121,814 patent/US5433261A/en not_active Expired - Lifetime
-
1994
- 1994-04-28 CA CA002157009A patent/CA2157009A1/en not_active Abandoned
- 1994-04-28 WO PCT/US1994/004806 patent/WO1994025199A1/en active IP Right Grant
- 1994-04-28 US US08/535,121 patent/US5884688A/en not_active Expired - Fee Related
- 1994-04-28 EP EP94915969A patent/EP0695226B1/en not_active Expired - Lifetime
- 1994-04-28 DE DE69404456T patent/DE69404456T2/en not_active Expired - Fee Related
- 1994-04-28 JP JP6524607A patent/JPH08509665A/en not_active Ceased
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2970982A (en) * | 1961-02-07 | Diorganopolysiloxanes of low vola- | ||
US2515628A (en) * | 1946-03-16 | 1950-07-18 | Du Pont | Aliphatic-cyano-azo compounds |
US2492763A (en) * | 1946-10-30 | 1949-12-27 | Du Pont | Azobis (alpha-cycloalkyl-acetonitriles) |
US3093494A (en) * | 1961-06-12 | 1963-06-11 | Dow Corning | Preparation of molded articles |
US3432312A (en) * | 1965-09-08 | 1969-03-11 | Howmet Corp | Refractory mold composition and method |
US4076685A (en) * | 1972-01-25 | 1978-02-28 | Ashland Oil, Inc. | Cyanoacrylate foundry binders and process |
US3898090A (en) * | 1974-06-24 | 1975-08-05 | Dow Corning | Foundry mold and core compositions |
US4357165A (en) * | 1978-11-08 | 1982-11-02 | The Duriron Company | Aluminosilicate hydrogel bonded granular compositions and method of preparing same |
US4526219A (en) * | 1980-01-07 | 1985-07-02 | Ashland Oil, Inc. | Process of forming foundry cores and molds utilizing binder curable by free radical polymerization |
US4602069A (en) * | 1984-04-11 | 1986-07-22 | Ashland Oil, Inc. | Phenolic resin-polyisocyanate binder systems containing a phosphorus based acid |
US4775704A (en) * | 1987-04-22 | 1988-10-04 | Teiji Nagahori | Mold material for forming sandmold without requiring mold wash |
US4894254A (en) * | 1987-11-17 | 1990-01-16 | Tokyo Ohka Kogyo Co., Ltd. | Method of forming silicone film |
US5167271A (en) * | 1988-10-20 | 1992-12-01 | Lange Frederick F | Method to produce ceramic reinforced or ceramic-metal matrix composite articles |
US4929704A (en) * | 1988-12-20 | 1990-05-29 | Hercules Incorporated | Isocyanate- and isothiocyanate-modified polysilazane ceramic precursors |
US5021533A (en) * | 1988-12-20 | 1991-06-04 | Hercules Incorporated | Crosslinkable poly(thio)ureasilazane composition containing a free radical generator |
US5138014A (en) * | 1988-12-20 | 1992-08-11 | Mitsubishi Kasei Corporation | Silicate compound modified by hydroxyl containing compounds |
US5183096A (en) * | 1990-03-15 | 1993-02-02 | Cook Arnold J | Method and apparatus for single die composite production |
Cited By (45)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5837047A (en) * | 1996-12-11 | 1998-11-17 | Ashland Inc. | Heat curable binder systems and their use |
US6147138A (en) * | 1997-06-06 | 2000-11-14 | Generis Gmbh | Method for manufacturing of parts by a deposition technique |
US20040250653A1 (en) * | 1999-07-20 | 2004-12-16 | Dwivedi Ratnesh K. | Microporous metal parts |
US7682704B2 (en) | 1999-07-20 | 2010-03-23 | Southco, Inc. | Microporous metal parts |
US20030233923A1 (en) * | 2002-06-20 | 2003-12-25 | Eu-Pin Wang | Woodworking drill |
US20080158173A1 (en) * | 2007-01-03 | 2008-07-03 | Apple Computer, Inc. | Multi-touch surface stackup arrangement |
US10226919B2 (en) | 2007-07-18 | 2019-03-12 | Voxeljet Ag | Articles and structures prepared by three-dimensional printing method |
US10960655B2 (en) | 2007-07-18 | 2021-03-30 | Voxeljet Ag | Articles and structures prepared by three-dimensional printing method |
US20090282528A1 (en) * | 2008-05-09 | 2009-11-12 | Monsanto Technology Llc | Plants and seeds of hybrid corn variety ch619141 |
US9656423B2 (en) | 2010-03-31 | 2017-05-23 | Voxeljet Ag | Device and method for producing three-dimensional models |
US9815243B2 (en) | 2010-03-31 | 2017-11-14 | Voxeljet Ag | Device for producing three-dimensional models |
US9962885B2 (en) | 2010-04-14 | 2018-05-08 | Voxeljet Ag | Device for producing three-dimensional models |
US9914169B2 (en) | 2010-04-17 | 2018-03-13 | Voxeljet Ag | Method and device for producing three-dimensional models |
US10639715B2 (en) | 2010-04-17 | 2020-05-05 | Voxeljet Ag | Method and device for producing three-dimensional models |
US10179365B2 (en) | 2010-04-17 | 2019-01-15 | Voxeljet Ag | Method and device for producing three-dimensional models |
US9770867B2 (en) | 2010-12-29 | 2017-09-26 | Voxeljet Ag | Method and material system for building models in layers |
US9649812B2 (en) | 2011-01-05 | 2017-05-16 | Voxeljet Ag | Device and method for constructing a laminar body comprising at least one position-adjustable body defining the working area |
US10220567B2 (en) | 2012-03-06 | 2019-03-05 | Voxeljet Ag | Method and device for producing three-dimensional models |
US10589460B2 (en) | 2012-03-06 | 2020-03-17 | Voxeljet Ag | Method and device for producing three-dimensional models |
US9863254B2 (en) | 2012-04-23 | 2018-01-09 | General Electric Company | Turbine airfoil with local wall thickness control |
US10059062B2 (en) | 2012-05-25 | 2018-08-28 | Voxeljet Ag | Device for producing three-dimensional models with special building platforms and drive systems |
US11225029B2 (en) | 2012-05-25 | 2022-01-18 | Voxeljet Ag | Device for producing three-dimensional models and methods thereof |
US10059058B2 (en) | 2012-06-22 | 2018-08-28 | Voxeljet Ag | Device for building a multilayer structure with storage container or filling container movable along the dispensing container |
US10052682B2 (en) | 2012-10-12 | 2018-08-21 | Voxeljet Ag | 3D multi-stage method |
US11097469B2 (en) | 2012-10-15 | 2021-08-24 | Voxeljet Ag | Method and device for producing three-dimensional models with a temperature-controllable print head |
US11130290B2 (en) | 2012-11-25 | 2021-09-28 | Voxeljet Ag | Construction of a 3D printing device for producing components |
US10213831B2 (en) | 2012-11-25 | 2019-02-26 | Voxeljet Ag | Construction of a 3D printing device for producing components |
US11072090B2 (en) | 2013-02-28 | 2021-07-27 | Voxeljet Ag | Material system for producing a molded part using a water-soluble casting mold |
US10343301B2 (en) | 2013-02-28 | 2019-07-09 | Voxeljet Ag | Process for producing a moulding using a water-soluble casting mould and material system for the production thereof |
US10786945B2 (en) | 2013-10-30 | 2020-09-29 | Voxeljet Ag | Method and device for producing three-dimensional models using a binding agent system |
US11541596B2 (en) | 2013-10-30 | 2023-01-03 | Voxeljet Ag | Method and device for producing three-dimensional models using a binding agent system |
US11850796B2 (en) | 2013-12-02 | 2023-12-26 | Voxeljet Ag | Interchangeable container with moveable side walls |
US11292188B2 (en) | 2013-12-02 | 2022-04-05 | Voxeljet Ag | Interchangeable container with moveable side walls |
US10220568B2 (en) | 2013-12-02 | 2019-03-05 | Voxeljet Ag | Interchangeable container with moveable side walls |
US9943981B2 (en) | 2013-12-11 | 2018-04-17 | Voxeljet Ag | 3D infiltration method |
US10442170B2 (en) | 2013-12-20 | 2019-10-15 | Voxeljet Ag | Device, special paper, and method for producing shaped articles |
US10889055B2 (en) | 2013-12-20 | 2021-01-12 | Voxeljet Ag | Device, special paper, and method for producing shaped articles |
US11097471B2 (en) | 2014-03-31 | 2021-08-24 | Voxeljet Ag | Method and device for 3D printing using temperature-controlled processing |
US10913207B2 (en) | 2014-05-26 | 2021-02-09 | Voxeljet Ag | 3D reverse printing method and device |
US10946556B2 (en) | 2014-08-02 | 2021-03-16 | Voxeljet Ag | Method and casting mold, in particular for use in cold casting methods |
US10682809B2 (en) | 2014-12-22 | 2020-06-16 | Voxeljet Ag | Method and device for producing 3D moulded parts by means of a layer construction technique |
US10843404B2 (en) | 2015-05-20 | 2020-11-24 | Voxeljet Ag | Phenolic resin method |
US10882110B2 (en) | 2015-09-09 | 2021-01-05 | Voxeljet Ag | Method and device for applying fluids |
US11890810B2 (en) | 2015-09-16 | 2024-02-06 | Voxeljet Ag | Device and method for producing three-dimensional shaped parts |
US11235518B2 (en) | 2015-12-01 | 2022-02-01 | Voxeljet Ag | Method and device for producing three-dimensional components with the aid of an overfeed sensor |
Also Published As
Publication number | Publication date |
---|---|
JPH08509665A (en) | 1996-10-15 |
DE69404456T2 (en) | 1997-12-04 |
EP0695226B1 (en) | 1997-07-23 |
CA2157009A1 (en) | 1994-11-10 |
WO1994025199A1 (en) | 1994-11-10 |
DE69404456D1 (en) | 1997-08-28 |
US5884688A (en) | 1999-03-23 |
EP0695226A1 (en) | 1996-02-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5433261A (en) | Methods for fabricating shapes by use of organometallic, ceramic precursor binders | |
US7732526B2 (en) | Silicone binders for investment casting | |
US4127157A (en) | Aluminum phosphate binder composition cured with ammonia and amines | |
US5641817A (en) | Methods for fabricating shapes by use of organometallic, ceramic precursor binders | |
US4127629A (en) | Process of forming silicon carbide bodies | |
US3688832A (en) | Refractory cores | |
US4209056A (en) | Aluminum phosphate binder composition cured with ammonia and amines | |
JPH07508255A (en) | Vibratable resin-bonded refractory composition | |
US3485288A (en) | Method of making a mold for casting of refractory and reactive metals | |
JPS60171269A (en) | Manufacture of complicated shape silicon nitride sintered body | |
WO1990002773A1 (en) | Foundry binder systems based upon acrylated epoxy resins and epoxy resins | |
GB2030065A (en) | Slip casting | |
US5703144A (en) | Solid furan binders for composite articles | |
JP3251937B2 (en) | Manufacturing method of sintered ceramic compact | |
JP6984926B1 (en) | Method for manufacturing metal-based composite material and method for manufacturing preform | |
GB2032898A (en) | Non-fired silicon carbide refractories | |
JPS612507A (en) | Porous durable mold and manufacture thereof | |
US2997759A (en) | Shell molding mixture | |
JPS58145330A (en) | Mold coating material for casting mold having microwave hardenability | |
WO2005021188A2 (en) | Compositions and use of sand and powders capable of being heated by microwave or induction energy | |
JPS6120506B2 (en) | ||
JPS60131858A (en) | Manufacture of basic refractories | |
JPH0517835A (en) | Production of preform for composite material | |
JP2000290075A (en) | Production of silicon carbide ceramics | |
JPS62270458A (en) | Method of forming sintered body and composition therefor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: LANXIDE TECHNOLOGY COMPANY, LP, DELAWARE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HINTON, JONATHAN WAYNE;LUKACS, ALEXANDER III;JENSEN, JAMES ALLEN;AND OTHERS;REEL/FRAME:006773/0210;SIGNING DATES FROM 19931101 TO 19931111 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
REMI | Maintenance fee reminder mailed | ||
FPAY | Fee payment |
Year of fee payment: 4 |
|
SULP | Surcharge for late payment | ||
AS | Assignment |
Owner name: KION CORPORATION, OHIO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:LANXIDE TECHNOLOGY COMPANY, LP;REEL/FRAME:011731/0697 Effective date: 20010427 |
|
FEPP | Fee payment procedure |
Free format text: PAT HOLDER CLAIMS SMALL ENTITY STATUS, ENTITY STATUS SET TO SMALL (ORIGINAL EVENT CODE: LTOS); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
AS | Assignment |
Owner name: CLARIANT CORPORATION, NORTH CAROLINA Free format text: MERGER;ASSIGNOR:KION CORPORATION;REEL/FRAME:018039/0327 Effective date: 20060331 |
|
AS | Assignment |
Owner name: CLARIANT INTERNATIONAL LTD., SWITZERLAND Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CLARIANT CORPORATION;REEL/FRAME:018039/0498 Effective date: 20060428 |
|
FEPP | Fee payment procedure |
Free format text: PAT HOLDER NO LONGER CLAIMS SMALL ENTITY STATUS, ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: STOL); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
AS | Assignment |
Owner name: CLARIANT FINANCE (BVI) LTD., VIRGIN ISLANDS, BRITI Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CLARIANT INTERNATIONAL LTD.;REEL/FRAME:018688/0788 Effective date: 20060829 |
|
FPAY | Fee payment |
Year of fee payment: 12 |